Apparatus for manufacturing halogen products of hydrocarbons.



B. S. LACY.

APPARATUS FOR MANUFACTURING HALOGEN PRODUCTS 0F HYDROCARBONS. APPLICATION FILED MAR. 3!. 19m.

Patented Apr. 23, 1918.

nnnnIr-r s. IiAGY, or snwnnr, nnw rnnsnr', nssrenon. TO THE nonssnnn & Hass- LACHER CHEMICAL company, or nrnw form, it. n, n coiaro i=1.

- rt t 11111.

T101 NEW YORK.

APPA 'IUS JEOJR. MANUFACTURING HALOGEN PRODUCTS U1? RUGA tONS.

mcaaoc. g

' Specification of Lettersfatent. Y watmnltjoetlldplt. 23, T911.

: @riginal application filed October 8, 1915, Serial No. 54,321, Divided and this application filed March 31,

1917. Serial ITO-158,975.

To all whom it may concern Be it known that I, Bunnrrr S. LAC a citizen of the United States of America, and a resident of Sewaren, in the county of Mid- .dlesex and State of New Jersey, have invented certain new and useful Improvements 1n Apparatus for ManufacturingHalogen Products of Hydrocarbons, ofwhich the following is a specification.

The invention relates to manufacturing halogen products of hydrocarbons and it relates particularly to the manufacture of chlorin-pro'ducts ofhydrocarbons, the object of the invention being to simplify the operation of the process and to safeguard the reaction against the formation of undesirable .byeproducts.

I shall describe my. invention, by way of example, as applied to the particular art of chlorinating methane, the same general ap paratus and method being also applicable to the chlorination of many other substances, for example, ethane and methylene chlorid, as well as to the halogenation of hydrocarbons in'general. This application is a dioperation is to mix the chlorin and methane in the cold and then pass the mixture into the heated reaction vessel, which, as described in U. S. Patent No. 1,111,842, maybe of silica, brick or other suitable material, but

of course, not of a material which like most metals, is readily attacked by hot chlorin. 7 There are, however, disadvantages connected with the use of non-metallic sub-- stances like silica or brick, more especially the. difficulty of making and maintaining them gas-tight under the temperature involved in the chlorination vessel. 0n the other hand, most metalsare more or less attacked by hot chlorin, or'they have an unfavorable action in that they tend to catalyzethe reaction.

the material and the harmful influences of the products formed thereby as well as to provide a chlorin-resistant lining in a gastight metallic shell serving as a reaction chamber, as will be further described below.

The apparatus consists therefore of a cylindrical iron shell 1 with a lining 2 composed of an acid tile brick or of silica, as

for instance of a section of a silica pipe.

This space between shell 1 and lining 2 is filled up with finely ground flint 3 which is nearly puresilica. The shell 1 is surrounded by a furnace 4 withsuitable flues 5, said flues being divided bypartitions 6 into separate heating compartments which serve to heat the shell by the burning therein, for instance of gas, supplied by pipes 7 ,the combustion gases leaving through exhit pipes 8.

The shell 1 is connected to a silica pipe 9 which is surrounded by an iron pipe 10. the space between the two pipes being filled with ground flint, pipe 9 extending up into space within the shell. The iron pipe 10 is attached to the iron T-piece 11, through which passes another sillica pipe 12 the lower portionof which is covered byan iron pipe 13, pipe 12 extending up into pipe 9; the outer end of silica pipe 12 is connected through an iron pipe 14 with the-iron T- -piece 15, which is fitted with the pipe 16.

The' connections between 11 and 13 and between 12 and 14' are made gas tight by rub.-

ber tubing, cement or other suitable means.

. Thebranch of T-piece 11 is connected to a ane current may be diverted through the valve 20 into the T-piece 15 where it mixes with the chlorinand passes on through the silica pipe 12. p

The remainder of the methane current passes on through the heater 17 into the silica pipe 9, in which at the orifice of the silca pipe 12 it meets the chlorin-containing gas. The total gas mixture enters the shell 1 through the silica pipe 9, and leaves the shell 1 through the iron pipe 22;

The wall through which the exit pipe 22 passes may be left unprotected by acid brick or ground flint, since in the gasses which come in contact with it the proportion of free unreacted chlorin is extremely small.

In case of need of such protection, such a lining may be easily provided by a plate 23 of material resistant to the corrosive action.

Where necessary to avoid heat losses, for example in connection with pipe 10 and T- piece 11 a covering of asbestos or other suitable heat insulating material maybe employed.

If now chlorin alone were passed through the reaction vessel as above described, the tendency ofthe powdered flint would, it is true, be to hinder the diffusion of the chlorin through to the iron shell; nevertheless, at the high temperature of the furnace more or less chlorin would come .in contact with the shell with consequent corrosion of the latter in the course of time. In the case of chlorination of methane, however, I have found that this is practically prevented,

for durin the progress of the gas mixture through t e layer 3 of flint powder at the bottom of shell 1, complete reaction ofthe chlorin occurs. Consequently when the gas mixture reaches the surface of the shell, practically no free chlorin remains, but only combined chlorin in the form. of hydrochloric acid, which, as is well known, has

little or no effect on iron at temperatures around 400 C.

The reaction vessel as shown in Figure 1 is provided with suitable means, such as gas pipes .7, in the flues 5 for heating. the lron shell. Thelayer 3 of powdered flint however, and the lining 2 itself, are poorconductors of heat; consequently it is not as easy nor as economical to furnish the heat necessary to bring the current of reaction gas up to the reaction temperature as it would be if a simple iron vessel could be employed.

As was stated in my Patent No. 1,190,659 by using a reaction mixture containing 4 to 6 volumes of methane to 1 volume of chlorin gas, the heat of the chemical reaction itself is sufficient to warm up the reaction mixture to the reaction temperature. When, however, it is desired to restrict the product essentially to monochlormethane, a larger proportion of methane, for example 15 volumes methane to 1 volume of chlorin gas,

is necessary; but the heat of the reaction is now,suflicient to heat up the gas mixture to only about 200 0. instead of to the required 400 C. or more; consequently efforts must be made to overcome the shortage in the reaction heat by some other means.

While trying to solve this problem, I found that preheating the applied methane aflords a convenient and economical means for accomplishing the desired result; for, since hot methane (in the absence of chlorin) has no effect on metals such as iron or copper, the methane may be heated with great ease by passing it through a metal vessel which is maintained at a suitable temperature.

In pursuance of this idea I preheated methane to about 260 in a copper pipe, but at its subsequent mixing with the chlorin I encountered a serious difliculty, namely the tendency toward the formation of a flame of chlorin at the orifice of the introduction pipe, theflame burning in the methane at the mixing point. When the reaction once strikes back from the furnace proper, which it tends to do even with the above mentioned degree of preheating, a chlorin flame in methane is produced, and when produced maintains itself as long as the chlorin is passed. This phenomenon is ac- Y companied by a total change in the character of the reaction. That is, instead of the smooth reaction (free from deposition of carbon),as follows:

together with a small amount of the react1on 'which may have been going on, We have a sudden change to the reactlon CH ,+2C1,=C+2HC1 aeaoa of tl1e15 volumes of mete is introduced through valve 20 into 'l-piece 15, where it mixes while still at ordinary temperature, with the 1 volume of chlorin admitted through pipe. 16, and the resultant mixture- 1s then passed through the silica pipe 12 into the silica pipe 9 entering the Shell 1. "When the mixture of 5 methane to 1 chlorin enters pipe 9 it meets there the current of 10 volumes of methane, which has been preheat-ed to about 370 C. in the heater 17, whereby a total mixture of 15 volumes of methane to 1 volume chlorin at a tempera? ture. of about 250 C. is obtained, but the formation of a chlorin flame is now completely prevented; the reaction going on between the constituents is perfectly smooth and the deposition of carbon does not take place.

By referring to the accompanying draw-.

ing, which represents an upright. furnace, it will be easily understood that the layer of ground flint between shell 1 and 2 as Well as at the bottom of shell 1 will settle down and automatically stop up any cracks which form in or between the bricks, and thus atall times make it impossible for currents of gas to pass outward to the iron shell. 7 i

The gas heating merely serves to balance radiation losses, external heat being thus nal heat which has to-be appliedto the iron suell may of course be decreased, or even bedispensed with entirely. If the situation permits this modification of the reaction furnace the co is easily performed by omitting from the construction shown in the accompanying drawing, the partitions 0, the gas supply pipes 7 and the em't pipes 8 and filling the empty due 5 for instance either by regular brick work, as that of furnace walls 4, or by filling in, instead of such added brick work, sand, infusorial earth or some other simllar insulating material;

since in case, if the walls of thefurnace are made of a-substantial thickness, the reaction gases will cool down by only a few degrees this loss may be compensated for by a slightly. higher degree of preheating.

Consequently no heat whatever need pass through the w of the reaction vessel,

from. which it follows that the layer of the reaction temperature, for this powdered silica may-be rather thick without afl'ecting the eficiency of the'process. The inside temperature of the reaction vessel naturally 7 increases progressively from the orifice of pipe 12, which is, in the above example, at a temperature of about 250 up to the point, which may be about the middie of the furnace, where the reaction has practically completed itself as far as appreciable evolution of heat is concerned;, at this point the temperature in the gas mixture is about 450 6., and the temperature of the corresponding part of the outside of the iron shell as well as the remainder of the furnace is maintained at about the same temperature, for instance between 4: 0500. (3., thus allowing the completion 0 the reaction, by which it may be insured that only a trace, for example. 0.01% or even less, of

the original chlorin remains unreacted.

lFurt rmore the above arrangement easily permits rapid variation as desired in the temperature of the ,gases in the reaction vessel; thus by opening valve 20 wider, a smaller proportion of the methane is preheated, consequently the temperature of the total gas mixture where it enters the. reaction vessel through the pipe 9, will immediately drop; the final temperature to which the gases are brought by the heat of reaction will of course, also be reduced. In

this manner by means of the valve 20, as well as by regulation of the temperature to which the methane is preheated in the heater 4 17 the temperatures produced in the reaction vessel may be controlled within wide in .I e i the application of my invenh'on to the chlorination of methane, l do not limit myself to the case of methane onto the particular conditions described in the foregoing, as it is obvious t the 1:. a princles may be employed in the chlorination ethane and other hydrocarbons aswell as in such procthe foregoing, have described if esses as the chlorinafion of eylene chlo-' I'lll, 3,000 I? m 1 my. copending application Serial #852,163, filed July 21, 1014, as well as to processes of halogenating hydrocarbons. ln naralf,

to the method described in process varies from 300 to 500 C. and the preheating may therefore be conveniently arranged to allow the operation of these processes according to-the method disclosed above. Neither do l restrict myself to the details of scribed, r I. the scope of the appended claims Ml w w l[ cl:

1. An apparatus for the reaction between corrosive and non-corrosive gases yielding the apparatus as shown anddenon-corrosive reaction products, consisting of furnace walls, an iron shell, a hea arrement between said shell and furnace walls, a lining within the shell resistant to the action of the corrosive gases, an inlet pipe to the shell, said pipe being of material resistant to the action of the corrosive gases and an'exit from said shell.

2. An apparatus for the reaction between corrosive and non-corrosive gases yielding non-corrosive reaction products, consisting of a furnace, an iron shell, flues between said shell and furnace, partitions to divide the flues into different compartments, a

burner for burning gas and an exit for combustion gases in each compartment, a lining within the shell of material resistant to the action of the corrosive gas, a filler resistant to the action of the corrosive gas betweenthe lining and the shell, an inlet pipe of resistant material and an exit pipe of material resistant to the action of the corrosive gases between the lining and the shell, an inlet pipe of material resistant to the action of the corrosive gases protected by an iron pipe, closed by a T-piece and a filler of material resistant to the action of the corrosive gases between both pipes, the

same being remote from the efi'ect of the ing the head of the aforesaid iron pipe with a preheating system having an inlet pipe and an introduction pipe of material rc- 1 sistan't to the action of the corrosive gases passing into the aforesaid inlet and con- .nected with the inlet pipe of the preheating system. v

4. An apparatus for the reaction between corrosive and non-corrosive gases yielding non-corrosive reaction products, consisting of furnace walls of substantial thickness, an iron shell, a lining within the shell resistant to the action of the corrosive gases, a filler of material resistant to the action of the corrosive gases between the linin and the shell, an inlet pipe of material resistant to the action of the corrosive gases protected by an iron pipe, closed by a T-piece and a filler of material resistant to the action of the corrosive gases between both pipes, the same being remote from the effect of the heating arrangement, a branch pipe connecting the head of the aforesaid iron pipe with a preheating system having an inlet pipe and an introduction pipe of material resist-. ant to the action of the corrosive gases passing into the aforesaid inlet and connected with the inlet pipe or the preheating system.

In testimony whereofI have signed this specification.

BURRITT S. LACY. 

